Thiazolyl-2, dimethyl carbamates



Patented June 22, 1954 THIAZOLYL-Z, DIMETHYL CARBAMATES Hans Gysin,Alfred Margot, and Charles Simon, Basel, Switzerland, assignors to J. R.Geigy A. G., Basel, Switzerland, a Swiss firm No Drawing. ApplicationDecember 9, 1952, Serial No. 325,015

Claims priority, application Switzerland August 22, 1949 3 Claims. 1

This application is a continuation-in-part of our pending applicationSer. No. 178,986 filed August 11, 1950.

The present invention is concerned with thiazolyl-(2)dimethyl carbamatesof the general formula:

wherein R and R. represent radicals selected from the group consistingof hydrogen and lower alkyl. These compounds are excellently suited forcombatting pests such as insects, especially flies, and other arthropodsand also their stages of development.

The new compounds can be produced, for example, by the reaction ofdimethyl carbamic acid chloride with 2-thiazolones of the generalformula wherein R and R have the meanings given above.

As such compounds may be named, e. g.: 4- methyl thiazolone-(Z)-ethyl-thiazolone-(Z), 4 n propyl-thiazolone-(Z), l-isopro-pyl-thiazmlone-(2), -n-butyl-thiazolone-(2), i-tert. butyl' thiazolone (2), 5methyl thiazolone-(z), 5- ethyl thiazolone- (2), 5-n-propylthiazolone-(2), 5 n butyl-thiazo1one-(2) efi-dimethyl-thiazolone (2), 4methyl-5-ethyl-thiazolone-(2), 4- methyl 5 n propyl-thiazolone-(Z),i-ethyl-5- methyl thiazo1one-(2) en-propyl-5-ethyl-thiazolone (2 4n-butyl-5-n-propyl-thiazolone- (2). The reaction may be performed in thepresence of acid binding agents or with salts of the enol form of theabove named compounds.

The reaction may take place in the presence or absence of solvents suchas benzene, acetone, dioxan, and acetic acid ethyl ester. Acid bindingagents which come into consideration are, e. g. potassium carbonate,sodium carbonate, sodium bicarbonate, sodium ethylate, or tertiaryorganic bases such as triethylamine. In particular, the alkali salts aresuitable as enol salts.

The following example illustrates the production of the new compounds.Parts are always given as parts by weight and the temperatures are givenin degrees centigrade.

Example 1 115 parts of l-methyl-thiazolone-(Z) are heated with 600 partsof benzene and 135 parts of potassium carbonate and the benzene isdistilled off until no more water passes over. The mixture is cooled andthen 120 parts of dimethyl carbainic acid chloride are added. Careshould be taken that the reaction does not take place too vigorously, bycooling if necessary. On completion of the reaction, the mixture isheated to boiling for 10-12 hours, and the Water which is so formed isremoved in a separator. The reaction mixture is then cooled, and 400parts of water and enough potassium carbonate solution is added so thatthe reaction of the watery solution definitely remains phenolphthaleinalkaline after thoroughly shaking with the benzene layer. Afterseparating off the watery part, the henzene solution is washed withwater until a neutral reaction is obtained, then the benzene isdistilled oii. After removal of some unchanged dimethyl carbamic acidchloride, the l-methylthiazolyl-(2)-dimethyl carbamate boils at 110- 112at 0.2 mm. pressure. In a pure form, the substance melts at In the samemanner, 5-methy1-thiazolyl-(2)- dimethyl carbamate and4.5-dimethyl-thiazolyl- (2) -dimethyl carbamate can be produced.

The biological properties of the new compounds are useful in variousfields of pest control and the mode of employment depends entirely onthe intended use. The active com-- pounds can be used as such, e. g. inpowder form, in the form of gas or mist or as smoke. For most purposes,however, it is more economical to combine them with suitable carriersand distributing agents. A number of such substances suitable for theusual forms of application such as dust ing agents, spraying agents(suspensions) solutions, aerosols, emulsions and semisolid preparations(ointments) are given below.

As solid pulverulent carriers may be used, e. g. calcium carbonate, inthe form of whiting or ground limestone, kaolin, bole, bentonite,talcum, powdered magnesia, kieselguhr, boric acid, tricalcium phosphate,and also powdered wood, powdered cork and other materials of a vegetablenature. By the addition of Wetting agents and protective colloids thepulverulent preparations can be suspended in water and use as sprayingagents. The active substance can be combined with the carrier forexample by impregnating the carrier with solutions of the activeingredient, by mixing the molten active ingredient with the carriers, orby milling the components together.

Solutions (for spraying) in high boiling carrier solvents such askerosene and similar mineral oil fractions, in methyl naphthalenes,

xylenes, etc. are best suited for direct spraying of objects. They canalso be used for impregnating Wood. Solutions in lower boiling solventssuch as trichlor-ethylene, tetrachlorethane, ethylene chloride are mostsuitable for spreading the active ingredient in the form of a mist. Thelatter solvents, and also, for example, benzine, xylene andchlorobenzene are also suitable for the impregnation of textiles. Theactive substances are soluble in water to some extent. Water, therefore,if required with the addition of solvents, also comes into considerationas a carrier-solvent and also water soluble organic solvents such asalcohol or acetone.

Fluoro-trichloromethane and difiuoro-dichloromethane are examples ofsolvents and propelling agents for aerosols.

As emulsifying agents there come into consideration those of acation-active nature such as quaternary ammonium compounds, anion-activeagents such as soap, soft soap, resin soap, aliphatic monoesters ofsulphuric acid and aliphatic aromatic sulphonic acids, and alsonon-ionogenic emulsifying agents such as higher molecular ethylene oxidecondensation products. The are mixed to an emulsifiable concentrationwith the active ingredient with or without the addition of suitablesolvents such as e. g. acetone, alcohols, cyclohexanone, benzene,toluene, xylene, tetrahydronaphthalene, alkylated naphthalenes, phthalicacid esters, mineral and vegetable oils, resins, and if desired, water.

Petroleum jelly and other ointment bases in which the active igredientcan be incorporated are examples of semi-solid distributing agents.

The active ingredients can also be used together with attractives orlures to form a bait, such as, e. g. sugar for example in the form ofdusting agents with sugar as the main carrier, or spraying agents or inthe form of fly-papers.

The various forms of application can generally be adapted to theintended use by the addition of substances which improve thedistribution, the adhesive properties and resistance to rain on thetreated surface, such as, e. g. fatty acids, resins, wetting agents,glue, casein or alginates. The biological activity can also be increasedby the addition of substances with bactericidal, fungicidal or alsoinsecticidal properties.

As bactericidal substances that can be added come into consideration, e.g. chlorinated phenols and quaternary ammonium compounds; suitablefungicidal compounds include e. g. sulphur in its various forms ofapplication, such as lime-sulphur liquid, copper compounds such ascopper oxychloride or Bordeaux liquid, and fluorides. As examples offurther insecticidal compounds may be namer. synthetic products like1.1-bis-(pchlorophenyl)2.2.2-trichlorethane, -hexachlorocyclohexane,p-nitrophenyl-diethyl-thiophosphate, tetra-ethyl-pyrophosphate,chlorinate cumphene, 12.4.5.6.7-8.8-octachloro4.7-methano-3a.4.7.la-tetrahydroindane, and5.5-dimethyl-dihydroresorcinol-dimethyl carbamate. Py-

rethrin and. rotenone are suitable vegetable products.

Example 2.Sprinlcling agent (spray) (a) 2 parts of active ingredient, e.g. a-methylthiazolyl-(2)-dimethyl carbamate are dissolved in 10 parts ofxylene and 88 parts of kerosene.

(b) 2 parts of active ingredient, e. g. 4-methylthiazolyl-(2) -dimethylcarbamate and 3 parts of 1.1-bis-(p-ch1orophenyl) 2.2.2 trichlorethaneare dissolved in 10 parts of xylene or another mutual solvent and 85parts of kerosene.

Both solutions are excellently suited for combatting flies in thehousehold and also in storerooms and slaughterhouses.

Example 3.Fumigating agent (a) 20 parts of active ingredient, e. g.il-methylthiazolyl-(Z) -dimethyl carbamate are mixed with 61 parts ofsawdust which has previously been impregnated with 18.4 parts ofpotassium nitrate. The mass is shaped into tablet form under pressure.

(b) parts of active ingredient, e. g. 4- methyl-thiazolyl-(2)-dimethylcarbamate, 22 parts of sugar, 12 parts of potassium chlorate, 2.4 partsof potassium nitrate and 13.6 parts of sawdust are ground and thoroughlymixed together. The mass is put into boxes and it is set alight byeither a wick or a fuse.

The insecticidal smoke formed by burning the tablets or the boxedfumigating mass is specially suitable for combatting insects in enclosedspaces.

Example 4.-Gas

-i methyl thiazolyl- (2) -dimethyl carbamate either as such or withsuitable additives which help vaporisation by heating, e. g. on anelectrically heated plate, is evaporated and in this way kills insectsin enclosed spaces.

What we claim is: 1. As new chemical compounds, the dimethyl carbamatesof the general formula:

RC'N CH: II H n'-c /COCO-N\ S OH: wherein R and R. represent radicalsselected from that group consisting of hydrogen and lower alkyl.

2. A pest cornbatting agent comprising as an active ingredient acompound of the general formula:

S CH3 wherein R and R represent radicals selected from the groupconsisting of hydrogen and lower alkyl.

3. As a new chemical compound, the i-methylthiazolyl- (2) -dimethylcarbamate.

No references cited.

1. AS NEW CHEMICAL COMPOUNDS, THE DIMETHYL CARBAMATES OF THE GENERALFORMULA: